Project title

Photocatalytic decontamination of pharmaceutic wastewaters using hybrid organic-inorganic magnetic supramolecular catalysts.

PharmPhotoMag

Project Code and number

PN-III-P4-ID-PCE-2020-2207; No. PCE235/2020

Contracting Authority

UEFISCDI

Project Host Institution

University of Bucharest

Run period

04.01.2021-31.12.2023

Total funding

1.198.032,00 lei

 

 

Research Team:

1. Bogdan Cojocaru - director

2. Madalina Sandulescu - researcher

3. Simona Coman – researcher

4. Vasile Parvulescu - researcher

5. Sabina Ion - PhD student

6. Nicolae Guzo – Master student

7. Razvan Mihailescu – Master student

8. Octavian Pavel – researcher

 

 

Project Summary

Along with the pharmaceuticals demand the related waste is more and more a problem. Both the low and high concentrations of the pharmaceutical pollutants are hazardous to the environment. The removal of these contaminants from waste waters requires efficient technologies. The aim of this project is the development of a laboratory validated method for visible light-driven photcatalytically decontamination of waters containing traces of β-lactam antibiotics using hybrid organic-inorganic magnetic supramolecular catalyst or a series of this kind of catalysts. The organic part of the hybrid will be represented by a metallic phthalocyanine, containing sulfonated groups, while the inorganic component of the hybrid system will be a LDH deposited on a magnetic substrate. In addition to the photocatalytic center, the hybrid materials will have basic sites that could co-operate with the photocatalytic reaction to yield the complete degradation of the organic compound, the magnetic substrate permitting easy recovery of the catalysts from the reaction environment. One of the innovative approaches will use the capacity of materials to firstly adsorb the noxious compounds. This project will bring new knowledge in the environmental chemistry by identifying efficient systems for environment remediation. The technology proposed to be investigated by the present project will use sun light as energy source. 

The main objective of this project is the development of a method to photcatalytically decontaminate waters containing low concentrations of β-lactam antibiotics using hybrid organic-inorganic magnetic supramolecular catalyst. The organic part of the hybrid will be represented by a metallo-phthalocyanine, while the inorganic component of the hybrid system will be a LDH deposited on a magnetic substrate.

 

 

The implementation degree of the project:

 

Phase I/2021 (04.01.2021–31.12.2021): Design of hybrid systems for photocatalytic mineralization of β-lactam antibiotics and determination photocatalytic performance (Budget 270.876 lei)

 

In order to achieve this phase, the following activities are carried out:

 

Activity 1.1. - Synthesis of phthalocyanine-LDH magnetic photocatalysts (with different LDH compositions);

Activity 1.2. - Preparation of magnetic hybrid photocatalysts by inserting phthalocyanine in LDH with different compositions;

Activity 1.3. - Preliminary tests with phthalocyanine-LDH magnetic photocatalysts in the photocatalytic degradation (mineralization) of β-lactam antibiotics in low concentration in water, under visible irradiation at different wavelengths or under sunlight.

 

Summary of the research report (Phase I):

Two series of catalysts PM@CuPc@(simple or containing Fe2+ or Fe3+)LDH and CuPc@( simple or containing Fe2+ or Fe3+)LDH @PM were prepared. Also Zn containing LDHs were prepared by three different methods in order to accommodate phthalocyanines and magnetic particles.

Characterization data asserted the success of the preparation. XRD data confirmed the LDH structure and the inter-layer insertion of magnetite; DR-UV-Vis, FT-IR and elemental analysis results showed the successful preparation of the materials and preservation of the LDH structure after phthalocyanine intercalation.

            The prepared catalysts exhibited a strong adsorptive capacity in only 10 min removing up to 50% of the antibiotic (oxacillin) under the dark conditions The photocatalytic activity under simulated sun-light conditions for the degradation of pure oxacillin (0.15mM) depended on the composition of LDH and preparation procedure. Thus, the catalysts from the PM@CuPc@(Fe2+ or Fe3+)LDH series exhibited the highest activity, with a complete removal in just 30 minutes.  The samples containing Fe3+-LDH exhibited the highest activity in both series. The degradation followed a pseudo first order reaction. The oxacillin degradation in a matrix of various components also containing a commercial drug was lower compared to pure oxacillin. Same trend was observed for ampicillin removal.

            All the objectives of this phase were achieved.

 

Dissemination

 

a.       Papers in scientific journals

1.      Rare-Earth-Modified Titania Nanoparticles: Molecular Insight into Synthesis and Photochemical Properties, Fredric G. Svensson, Bogdan Cojocaru, Zhen Qiu, Vasile Parvulescu, Tomas Edvinsson, Gulaim A. Seisenbaeva, Carmen Tiseanu, Vadim G. Kessler, Inorganic Chemistry, 2021, 60 (19), 14820–14830.

 

b.      International conferences

1.      New approaches in synthesis of 2D LDH-type materials used in the Claisen-Schmidt condensation, Silvana-Denisa Mihăilă, Bogdan Cojocaru, Bogdan Jurca, Octavian-Dumitru Pavel, Gheorghiţa Mitran, Rodica Zăvoianu, Vasile I. Pârvulescu, Contemporary Solutions for Advanced Catalytic Materials with a High Impact on Society (CoSolMat), 11th – 15th OCTOBER 2021, Bucharest, Romania (ORAL presentation);

2.      Photocatalytic decontamination of wastewaters using hybrid organic inorganic magnetic supramolecular catalysts, Razvan Mihailescu, Octavian D. Pavel, Sabina Ion, Madalina Tudorache, Simona M. Coman, Vasile I. Parvulescu, Bogdan Cojocaru, Contemporary Solutions for Advanced Catalytic Materials with a High Impact on Society (CoSolMat), 11th – 15th OCTOBER 2021, Bucharest, Romania (POSTER presentation).

 

 Phase II/2019 (01.01.2022-31.12.2022): Design of hybrid systems for photocatalytic mineralization of β-lactam antibiotics and determination of photocatalytic performance (Budget 631.606 lei)

 

In order to achieve this phase, the following activities are carried out:

 

 Activity 2.1. -  Preparation of phthalocyanine magnetic photocatalysts (insertion of phthalocyanines containing different metal ions) –LDH;

Activity 2.2. - Morphological, structural and functional characterization of visibly active photocatalytic composites

Activity 2.3. - Testing of phthalocyanine-LDH magnetic photocatalysts in photocatalytic degradation (mineralization) of β-lactam antibiotics in low concentration in water, under visible field irradiation at different wavelengths or under sunlight;

Activity 2.4. - Selection of photocatalysts with optimal performance.

 

Summary of the research report (Phase II):

Dissemination

 

 

Phase III/2020 (01.01.2023-31.12.2023): Development and optimization of the process of photocatalytic mineralization of pharmaceutical products under the influence of visible light (Budget 295.550 lei)

 

In order to achieve this phase, the following activities are carried out:

 

Activity 3.1. -  Testing of phthalocyanine-LDH magnetic photocatalysts in photocatalytic degradation (mineralization) of β-lactam antibiotics in low concentration in water, under visible field irradiation at different wavelengths or under sunlight;

Activity 3.2. - Additional preparations of phthalocyanine-LDH magnetic photocatalysts;

Activity 3.3. - Characterization of additional prepared phthalocyanine-LDH magnetic photocatalysts;

Activity 3.4. - Selection of photocatalysts with optimal performance.

 

Summary of the research report (Phase III):

Dissemination